CN109634021A - A kind of quasi- solid-state tungstic acid electrochromic device and preparation method thereof - Google Patents
A kind of quasi- solid-state tungstic acid electrochromic device and preparation method thereof Download PDFInfo
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- CN109634021A CN109634021A CN201811393517.6A CN201811393517A CN109634021A CN 109634021 A CN109634021 A CN 109634021A CN 201811393517 A CN201811393517 A CN 201811393517A CN 109634021 A CN109634021 A CN 109634021A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1523—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material
- G02F1/1525—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect characterised by the electrochromic material, e.g. by the electrodeposited material comprising inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/1533—Constructional details structural features not otherwise provided for
Abstract
The invention discloses a kind of quasi- solid-state tungstic acid electrochromic device and preparation method thereof, which includes: working electrode, electrolyte layer, to electrode, transparency conducting layer；Working electrode is tungsten oxide, and it is nano-cerium oxide to electrode that electrolyte layer, which is choline chloride ethylene glycol gel containing lithium salt,；The present invention is using spray coating method preparation Tungsten Trioxide Electrochromic Films electrode and cerium oxide to electrode, using gel electrolyte as class ionic liquid, have the characteristics that low in cost, environmentally protective, highly transparent, be not easy to reveal, ionic conductivity it is high, have the characteristics that fast response time, optical density (OD) difference are big, low in cost using device prepared by such electrolyte.
Description
Technical field
The invention belongs to electrochomeric films device preparation field, in particular to a kind of quasi- solid-state tungstic acid electrochromism
Device and preparation method thereof.
Background technique
Electrochromism refers to that the injection and extraction of electronics and ion occur under electrochemical action for material, makes its valence state and change
It learns component to change, so that the reflection of material and transmission performance be made to change, color and transparent is then shown as on appearance property
The reversible change of degree.Electrochromic material is divided into inorganic electrochromic material (transition metal oxide or derivatives thereof) and organic
Electrochromic material (purpurine class and conducting polymer).The performance of inorganic electrochromic material is stablized, light absorption variation be by
Caused by going out in the Dual Implantations and black soy sauce of ion and electronics, Typical Representative is tungstic acid, with WO3For the nothing of functional material
The industrialization of machine electrochromic device.And organic electrochromic material is rich in color, Yi Jinhang MOLECULE DESIGN, light absorption becomes
Change and come from redox reaction, but use temperature range is narrow, mainly there is polythiophene class and its derivative, purple sieve essence class, four sulphur
Fulvalene, metallo phthalocyanine etc. have obtained reality using purple sieve essence class as the organic electrochromic material of functional material
Using.
Electrochromic material can integrate in the device for adjusting its transmitance, reflectivity, absorptivity or emissivity.It is electroluminescent
The variation of Electrochromic device color between fading can be used to adjust solar radiation quantity.When it is under colored state, dress
A large amount of solar radiations can be absorbed by setting, and reduce the amount of incident of sunlight, so as to achieve the effect that temperature control.Electrochromic device master
To be applied to automobile anti-dazzle light rearview mirror and intelligent glass pane, referred to as smart window.In hot state, include by changing to be applied to
The voltage at electrochomeric films smart window both ends, smart window color become dark, stop passing through for light, while stopping sun spoke
The transmission of heat is penetrated, keeps room temperature lower than outdoor.Under cold state, change the voltage of smart window, makes its colour fading, return to
Bright state makes solar radiation be incident on interior, keeps indoor environment comfortable.
Wang et al. (DOI:10.1146/annurev-chembioeng-080615-034647;
Switchable Materials for Smart Windows) structure of general electrochromic device is summarized, for
Metal oxide-type electrochromic material, a complete electrochromic device, generally comprises (a) working electrode, and use is electroluminescent
Off-color material；(b) electrolyte layer is used for transmission ion；(c) to electrode, it is used as ion storage layer, improves electrochromic device
Performance；(d) transparency conducting layer is used for external power supply.
Application No. is 201210542576.1 Chinese patents to disclose a kind of electrochromic material and electrochromic device,
The electrochromic material includes the poly- electricity of cathode electrochromic material, anode electrochromic material, electrolyte and acrylate ionomer salt
The mixture of matter composition is solved, anode electrochromic material is 10 methyl phenothiazine, and the electrolyte is ethylene carbonate or γ-
Butyrolactone, electrochromic device include transparent glass, reflecting glass, and the surrounding of transparent glass and reflecting glass is viscous by adhesive
Conjunction forms cavity, and electrochromic material described above is filled with inside cavity；The patent electrochromic material is non-homogeneous
Electrically charged acrylate ionomer salt polyelectrolyte is added in electric field, keeps the color change of electrochromic material fast, but the electroluminescent change
The electrochromic device of color material preparation has cathode electrochromic material and anode electrochromic material after discoloration for a long time
Migration rate is extremely low, therefore fade rates are fast, but this device has the common disadvantage of organic electrochromic material ---
Durability is not strong, and especially under conditions of having ultraviolet light, organic electrochromic device can gradually degrade, and device is caused to colour
State generates bleaching, color contrast decline.
Application No. is 201510292210.7 patents to disclose a kind of electrochromic material and its electrochromic device,
The mixture that electrochromic material is made of cathode electrochromic material and anode electrochromic material, cathode electrochromic material
It is the general formula compound that various substituent groups are had on pyridine ring, it is intended to strengthen structure in colourshifting process and be changed by quadrature
Charge dispersibility in stability and pyridine ring when flat state, improves the potential difference Δ E value between two states；Patent electricity
Mutagens color device includes transparent conducting glass, conducting reflective glass, the transparency conducting layer and conducting reflective of transparent conducting glass
The conductive reflective of glass is oppositely arranged, and bonds to form chamber by colloid in the surrounding of transparent conducting glass and conducting reflective glass
Body, cavity is interior to be filled with the electrochromic material；With the long-life, discoloration and the fast feature of fade rates are applicable to
The smart window of anti-glare rear-view mirror for automobile field or dimming glass for building.The patented technology is using purpurine class cathodic electrochromic
Off-color material is mixed with organic anode electrochromic material, and purpurine class point to off-color material must be dissolved in liquid electrolyte
In solution, then seal, and liquid electrolyte is easy to happen leakage, safety is not high, limits its application.In general, existing
There is electrochromic material disclosed in technology, organic liquid electrolysis has the safety issues such as leakage；And inorganic solid electrolyte
Conductivity is low, and the response time is long, and practical application is difficult.
In addition, the patent is prepared using the method that current electrochromic device mostly uses magnetron sputtering, this method has
Film forming is good, the uniform advantage of film, is one of the common method of electrochomeric films preparation.But expensive equipment, it is very long
It vacuumizes and sputtering process, film morphology is difficult to control, and can prepare the finiteness of film size, limits magnetron sputtering system
The further development and commercialization of standby film promote and apply.
Summary of the invention
For existing electrochromic device, that there are cycle performances is bad, and coloration efficiency is low, and optical contrast is unobvious, response
The problem of time is long, preparation cost height etc. provides a kind of quasi- solid-state tungstic acid electrochromic device and preparation method thereof, this hair
It is bright to be achieved through the following technical solutions:
A kind of quasi- solid-state tungstic acid electrochromic device, from top to bottom successively are as follows: tungstic acid working electrode, gel electrolyte
Matter layer, cerium oxide are to electrode；The tungstic acid working electrode is the ito substrate 1 for spraying tungstic acid 2；The gel electrolyte
Matter layer includes gel electrolyte 3 and the silicagel pad 6 for being wrapped in 3 surrounding of gel electrolyte；The cerium oxide is spraying oxygen to electrode
Change the ito substrate 5 of cerium 4；Wherein, tungstic acid working electrode makees electrochromic layer, and electrolyte layer is used for transmission ion, cerium oxide
Ion storage or discoloration are used for electrode.
Further, gel electrolyte of the present invention is prepared by the following method: 1:2 is by choline chloride in molar ratio
It is dissolved in ethylene glycol solution, under nitrogen atmosphere, 40 DEG C are uniformly mixing to obtain clear transparent solutions, are added into clear transparent solutions double
Trifluoromethanesulfonimide lithium, forms the electrolyte solution that double trifluoromethanesulfonimide lithium concentrations are 0.1M, then to electrolyte
It is added 10% mass fraction hydrophilic silica in solution, the mass ratio of electrolyte solution and hydrophilic silica is 10:1；
Then it is dried 24 hours in 60 DEG C of vacuum ovens, that is, obtains the gel electrolyte.
The present invention additionally provides the preparation method of above-mentioned quasi- solid-state tungstic acid electrochromic device, specific steps simultaneously
It is as follows:
1) preparation of tungstic acid working electrode:
Step a: by (NH4)2SO4Na is added2WO4.2H2It in O solution, stirs evenly, hydrochloric acid is then added and adjusts PH to 2.0；
200 DEG C hydro-thermal reaction 48 hours, then 60 DEG C of dryings；Obtain WO3Nano wire；
Step b: to WO3Isopropanol is added in nano wire, ultrasonic disperse 2 hours, obtains WO3The WO that mass fraction is 0.5%3It mixes molten
Liquid；
Step c: by WO3Mixed solution is sprayed at ito substrate surface, sprays 0.2 mL/min of flow, and spray time 20 minutes；?
The WO for being about 400nm to thickness3Film；Ito substrate after spraying is put into electron tubes type furnace annealing, 400 DEG C of annealing temperature,
Annealing time 1 hour, i.e. acquisition tungstic acid working electrode, it is spare；
2) preparation of gel electrolyte:
Choline chloride is dissolved in ethylene glycol solution by 1:2 in molar ratio, and under nitrogen atmosphere, 40 DEG C are stirred 2 hours, obtains clear
Double trifluoromethanesulfonimide lithiums are added into clear transparent solutions for solution, form double trifluoromethanesulfonimide lithium concentrations and are
The electrolyte solution of 0.1M, is added 10% mass fraction hydrophilic silica, 3 g into electrolyte solution, electrolyte solution with
The mass ratio of hydrophilic silica is 10:1；Then it is dried 24 hours in 60 DEG C of vacuum ovens, that is, obtains the gel electricity
Xie Zhi；
3) preparation of the nano-cerium oxide to electrode:
Step a:2.5 g CeCl3.7H2O is dissolved in (CeCl in 60mL deionized water3.7H2The concentration of O is 0.1M), after stirring 2 h
Solution is transferred in 100 mL reaction kettles, hydrothermal temperature is 180 DEG C, and 12 h of time is collected by centrifugation, and after 60 DEG C of dryings, is obtained
Nano-cerium oxide powder；
Step b: isopropanol or ethyl alcohol being added into nano-cerium oxide powder, obtain nano-cerium oxide mass fraction be 0.5% it is mixed
Solution is closed, ultrasonic disperse 2 hours, obtains nano-cerium oxide mixed solution；
Step c: taking nano-cerium oxide mixed solution for spraying ito substrate, 0.2 mL/min of flow, and spray time 20 minutes；
Cerium oxide after spraying is made annealing treatment, 500 DEG C of annealing temperature, 1 h of soaking time；Nano-cerium oxide is obtained to electricity
Pole, it is spare；
4) assembling of electrochromic device:
The tungstic acid working electrode for taking step 1) to obtain, will contain WO3Coat binder on one side, then paste silicagel pad；To
The gel electrolyte that step 2 obtains is added in silicone gasket, is placed in drying box dry 30 min；In the another side of silicagel pad
Coated with adhesive, gluing steps 3) obtain nano-cerium oxide electrode is stained with, be compacted, at room temperature solidify 2 days, that is, obtained
Electrochromic device.
The present invention is prepared for a kind of quasi- solid-state tungstic acid electrochromic device, including spraying legal system using the method for spraying
Standby Tungsten Trioxide Electrochromic Films electrode and cerium oxide are to electrode；In contrast to general electrochromic device, the present invention have with
It is lower the utility model has the advantages that
1, simple process and low cost of the present invention can get rid of expensive traditional and complicated vacuum magnetic-control sputtering equipment,
And can large area preparation, can be used for the preparation of flexible electrode material.
2, nanometer threadiness tungstic acid is conducive to lithium ion from the porous network structure being wound in spraying process
Insertion and abjection, the chemical properties such as effective response speed, cycle life for improving electrochromic device.
3, the gel electrolyte that uses of the present invention is for class ionic liquid, with low in cost, environmentally protective, highly transparent,
It is not easy the feature revealed, ionic conductivity is high, the device using the preparation of such electrolyte has fast response time, optical density (OD) poor
Big feature.
4, the present invention, which prepares electrochomeric films using the method for spraying, can largely reduce cost, promote business
The development of change.
Detailed description of the invention
Fig. 1 is electrochromic device structural schematic diagram in embodiment 1；
Wherein, 1, ito substrate；2, tungstic acid；3, gel electrolyte；4, cerium oxide；5, ito substrate；6, silicagel pad；
Fig. 2 is the scanning electron microscope (SEM) photograph of 1 tungsten trioxide powder of embodiment；
Fig. 3 is that large area electrochromic device is colouring and the light transmittance curve under bleached state in embodiment 1；
Fig. 4 is the chronoa mperometric plot that Tungsten Trioxide Electrochromic Films measure under three-electrode system in embodiment 1；
Fig. 5 is the scanning electron microscope (SEM) photograph of 2 tungstic acid of embodiment；
Fig. 6 is the chronoa mperometric plot that Tungsten Trioxide Electrochromic Films measure under three-electrode system in embodiment 2；
Fig. 7 is the chronoa mperometric plot that Tungsten Trioxide Electrochromic Films measure under three-electrode system in embodiment 3.
Specific embodiment
Below with reference to specific implementation case, the present invention is further explained.It should be understood that these case study on implementation are merely to illustrate this
It invents rather than limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, this field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims institute
The range of restriction.
Raw material sources involved in embodiment:
Ito substrate: triumphant for company's production, ITO layer thickness about 300nm purchased from Zhuhai.Lithium perchlorate, acetonitrile, Disodium tungstate (Na2WO4) dihydrate,
Seven chloride hydrate ceriums, double trifluoromethanesulfonimide lithiums, hydrophilic silica are purchased from Aladdin company.
Sealant model meets -704 silicon rubber of light, and silica gel pad is purchased from oupli company.
Embodiment 1 prepares electrochromic device
1, the preparation of tungstic acid working electrode:
Step a: 3.3 g Na are taken2WO4.2H2O is dissolved in 76 mL deionized waters, and the concentration of sodium tungstate solution is 0.13M, to complete
2 g (NH are added after fully dissolved4)2SO4, hydrochloric acid is added and adjusts PH to 2.0.
Step b: the solution for taking 60 mL step a to obtain is placed in 100 mL reaction kettles, and forced air drying is put into after being sealed
Case carries out hydro-thermal reaction, and 200 DEG C are reacted 48 hours, then 60 DEG C of dryings；Obtain WO3Nano wire；The WO that this step obtains3It receives
Rice noodles scanning electron microscope (SEM) photograph is as shown in Fig. 2, WO3Nanowire diameter can form nanovoids structure in 50 nm or so, be conducive to from
Son insertion abjection, improves the cycle life of electrochromic device.
Step c: the WO for taking step b to obtain3Isopropanol is added in nano wire, forms the mixed solution that mass fraction is 0.5%,
Ultrasonic disperse 2 hours, obtain WO3Mixed solution.
Step d: the WO for taking step c to obtain3Mixed solution is for spraying ito substrate, the spray of spray gun model Taiwan Pola
Rifle RH-BS(0.3 bore), 0.2 mL/min of flow is sprayed, spray area is 3 × 3 cm2When spray solution dosage be 4 mL, spray
It applies the time 20 minutes,；Obtain the film that thickness is about 400nm；Ito substrate after spraying is put into electron tubes type furnace annealing, is moved back
400 DEG C of fiery temperature annealing time 1 hour, obtains tungstic acid working electrode, spare.
2, the preparation of gel electrolyte:
Choline chloride is dissolved in ethylene glycol solution by 1:2 in molar ratio, and choline chloride leads to nitrogen protection, and 40 DEG C are stirred 2 hours, is obtained
To clear transparent solutions；The above-mentioned clear transparent solutions of 30 mL are taken, under conditions of logical nitrogen protection, it is (double that LiTFSI lithium salts is added
Trifluoromethanesulfonimide lithium) 0.861 g, form the electrolyte solution that concentration is 0.1M；30 g electrolyte solutions are taken, in logical nitrogen
Under conditions of gas shielded, 10% mass fraction hydrophilic silica, 3 g is added, obtained solution is placed in 60 DEG C of vacuum drying
It is dried in case, 24 hours, obtains gel electrolyte containing lithium salt.
3, preparation of the nano-cerium oxide to electrode:
Step a:2.5 g CeCl3·7H2O is dissolved in 60mL deionized water, obtains the CeCl that concentration is 0.1M3·7H2O is molten
Solution is transferred in 100 mL reaction kettles by liquid after stirring 2 h, and hydrothermal temperature is 180 DEG C, 12 h of time, 7000 rpm/min,
5min is collected by centrifugation, and after 60 DEG C of dryings, obtains nano-cerium oxide powder；
Step b: ceria film is prepared to electrode using the method for spraying: step a being taken to obtain nano-cerium oxide powder, is added different
In propyl alcohol, ultrasonic disperse 2 hours, the mixed solution that mass fraction is 0.5% nano-cerium oxide is formed,；
Step c: for the mixed solution for taking step b to obtain for spraying ito substrate, 0.2 mL/min of flow is sprayed on area 3 × 3
cm2Ito substrate on, spray time 20 minutes；Cerium oxide after spraying is made annealing treatment, 500 DEG C of annealing temperature, is protected
Warm 1 h of time；
4, the assembling of electrochromic device, comprising:
(1) the tungstic acid working electrode for taking step 1 to obtain, will contain WO3One side upward, surrounding coats binder, pastes silicon
Rubber mat (thickness 1mm)；
The silica gel pad is only used for immobilized gel electrolyte, using the sizeable silicagel pad of conventional commercial, to the present invention
Experimental result do not have an impact.
(2) gel electrolyte that step 2 obtains is added into silicone gasket, is placed in drying box dry 30 min；It obtains
Electrolyte layer；The thickness of electrolyte layer depends on spacer thickness, this experiment electrolyte layer is with a thickness of 1 mm；(3) in silicagel pad
Another side coated with adhesive, the nano-cerium oxide for rapidly obtaining step 3 are stained with electrode, wherein cerium oxide is face-down, pressure
It is real, solidify 2 days at room temperature；Obtain electrochromic device.
The present embodiment electrochromic device structure obtained is as shown in Figure 1, be from top to bottom followed successively by ito substrate 1, three oxygen
Change tungsten 2, gel electrolyte 3, cerium oxide 4, ito substrate 5, and is centered around the silicagel pad 6 of 3 surrounding of gel electrolyte.
Fig. 3 is the present embodiment electrochromic device in coloring and the light transmittance curve schematic diagram under bleached state, Fig. 3, a
Curve is colored state, and b curve is bleached state；Transmitance mean difference is greater than 50% in visible spectrum, illustrates with this
The gel that embodiment obtains is that the electrochromic device of electrolyte preparation has good light modulation ability.
Fig. 4 is the chronoa mperometric plot that the present embodiment electrochromic device measures under three-electrode system；Three-electrode system
Measurement system；Working electrode is tungstic acid working electrode prepared by step 1, reference electrode Ag/Ag+Electrode is to electrode
The cm platinum plate electrode of cm × 0.1 of 10 cm × 10, electrolyte are 0.1M lithium perchlorate (LiClO4)/acetonitrile solution, pulse voltage:
± 1.0V, pulse width: 30 s, pulse number: 201, circulating ring number: 100 circles.When by calculating first lap and 100 circle most
Big coloring electric current assesses the attenuation degree of electrochomeric films performance with maximum colour fading electric current；It has no and declines after 100 circle circulations
Subtract, illustrates it with good cyclical stability.
Embodiment 2 prepares electrochromic device
In the present embodiment preparation method, except it is following prepare tungstic acid working electrode step in addition to, other steps with 1 phase of embodiment
Together.
Prepare tungstic acid working electrode:
Step a: 3.3 g Na are taken2WO4.2H2O is dissolved in 76 mL deionized waters, and salt acid for adjusting pH is added to 2.0.
Step b: taking the above-mentioned solution of 60 mL to be placed in 100 mL reaction kettles, and air dry oven progress is put into after being sealed
Hydro-thermal reaction, 200 DEG C of reaction temperature, the time 48 hours.By WO3It is collected by centrifugation, 60 DEG C of dryings.
Step c: the WO for taking step b to obtain3, isopropanol is added, forms WO3The mixed solution that mass fraction is 0.5%, ultrasound
Dispersion 2 hours obtains WO3Mixed solution, SEM figure are as shown in Figure 5, it is seen then that ammonium sulfate is not added and makees pattern controlling agent, three oxygen
Changing tungsten is in nano bar-shape, and 100 nm of diameter has clustering phenomena.
Step d: the solution after taking step c ultrasonic disperse is for spraying, spray gun model Taiwan Prona RH-BS
(0.3 bore), sprays 0.2 mL/min of flow, and spray area is 3 × 3 cm2When spray solution dosage be 4 mL, spray time
20 minutes；Ito substrate after spraying is put into electron tubes type furnace annealing, 400 DEG C of annealing temperature, annealing time 1 hour, is obtained
Tungstic acid working electrode.
Fig. 6 is 100 circle curve of electrochromic device tungstic acid electrode chrono-amperometric manufactured in the present embodiment circulation, is compared
In the nano wire that embodiment 1 obtains, cycle performance decline.
Embodiment 3 prepares electrochromic device
Except it is following prepare tungstic acid working electrode step in addition to, other steps are same as Example 1.
Prepare tungstic acid working electrode:
Step a: 3.3 g Na are taken2WO4.2H2O is dissolved in 76 mL deionized waters, and 2 g (NH are added until completely dissolved4)2SO4,
Hydrochloric acid is added and adjusts PH to 2.0.
Step b: taking the above-mentioned solution of 60 mL to be placed in 100 mL reaction kettles, and air dry oven progress is put into after being sealed
Hydro-thermal reaction, 200 DEG C of reaction temperature, the time 48 hours.Collect WO3Nano wire, 60 DEG C of dryings.
Step c: the WO for taking step b to obtain3Isopropanol is added in nano wire, forms the mixed solution that mass fraction is 0.5%,
Ultrasonic disperse 2 hours.
Step d: the solution after taking step c ultrasonic disperse is for spraying, spray gun model Taiwan Prona RH-BS
(0.3 bore), sprays 0.2 mL/min of flow, and spray area is 3 × 3 cm2When spray solution dosage be 2 mL, spray time
10 minutes；The film that thickness is about 200nm is obtained, the ito substrate after spraying is put into electron tubes type furnace annealing, annealing temperature
400 DEG C, annealing time 1 hour, obtain tungstic acid working electrode.
Fig. 7 is 81 circle Dependence Results of the circulation of electrochromic device tungstic acid electrode chrono-amperometric obtained in the present embodiment
Schematic diagram, it is seen that compared to embodiment 1, since spraying tungstic acid total amount is reduced, corresponding maximum coloring and colour fading electric current also subtract
It is small, but cycle performance is good.
There are many concrete application approach of the present invention, the above is only a preferred embodiment of the present invention, it is noted that for
For those skilled in the art, without departing from the principle of the present invention, several improvement can also be made, this
A little improve also should be regarded as protection scope of the present invention.
Claims (5)
1. a kind of quasi- solid-state tungstic acid electrochromic device, which is characterized in that the electrochromic device is from top to bottom successively
Are as follows: tungstic acid working electrode, gel electrolyte layer, cerium oxide are to electrode；The tungstic acid working electrode is three oxygen of spraying
Change the ito substrate (1) of tungsten (2)；The gel electrolyte layer includes gel electrolyte (3) and is wrapped in gel electrolyte (3) four
The silicagel pad (6) in week；The cerium oxide is the ito substrate (5) for spraying cerium oxide (4) to electrode.
2. quasi- solid-state tungstic acid electrochromic device according to claim 1, which is characterized in that the gel electrolyte is
Be prepared by the following method: choline chloride is dissolved in ethylene glycol solution by 1:2 in molar ratio, under nitrogen atmosphere, is stirred evenly, is added
Enter double trifluoromethanesulfonimide lithiums, forms the electrolyte solution that double trifluoromethanesulfonimide lithium concentrations are 0.1M；It adds
The mass ratio of the hydrophilic silica that mass fraction is 10%, electrolyte solution and hydrophilic silica is 10:1；Then true
Sky is dry, that is, obtains the gel electrolyte.
3. the preparation method of quasi- solid-state tungstic acid electrochromic device as claimed in claim 1 or 2, the specific steps of which are as follows:
1) preparation of tungstic acid working electrode:
By (NH4)2SO4Na is added2WO4.2H2In O solution, PH to 2.0 is adjusted, it is dry after hydro-thermal reaction 48 hours, obtain WO3It receives
Rice noodles；Then isopropanol is added, ultrasonic disperse obtains WO3Mixed solution；By WO3Mixed solution is sprayed at ito substrate surface, spray
Apply 0.2 mL/min of flow, spray time 10-20 minutes；400 DEG C are annealed 1 hour, i.e. acquisition tungstic acid working electrode, standby
With；
2) preparation of gel electrolyte:
Choline chloride is dissolved in ethylene glycol solution by 1:2 in molar ratio, and under nitrogen atmosphere, 40 DEG C are stirring evenly and then adding into double fluoroforms
Alkane sulfimide lithium forms the electrolyte solution that double trifluoromethanesulfonimide lithium concentrations are 0.1M, adds into electrolyte solution
Enter 10% hydrophilic silica of mass fraction, the mass ratio of electrolyte solution and hydrophilic silica is 10:1；Then 60 DEG C
It is dried 24 hours in vacuum oven, that is, obtains the gel electrolyte, it is spare；
3) preparation of the nano-cerium oxide to electrode:
The CeCl for being 0.1M by concentration3.7H2180 DEG C of 12 h of hydro-thermal reaction of O solution, centrifugal drying obtain nano-cerium oxide powder；
Isopropanol or ethyl alcohol is added, ultrasonic disperse obtains the mixed solution that nano-cerium oxide mass fraction is 0.5%；Take mixed solution and sprayed
Applying ito substrate, 0.2 mL/min of flow spray time 20 minutes, 500 DEG C of 1 h of annealing, that is, obtains nano-cerium oxide to electrode,
It is spare；
4) assembling of electrochromic device:
The tungstic acid working electrode for taking step 1) to obtain, will spray WO3Coat binder on one side, then paste silicagel pad；To
The gel electrolyte that step 2 obtains is added in silicone gasket and pastes step in the another side coated with adhesive of silicagel pad after drying
The rapid nano-cerium oxide 3) obtained solidifies at room temperature to electrode, compacting, that is, obtains quasi- solid-state tungstic acid electrochromic device.
4. the preparation method of quasi- solid-state tungstic acid electrochromic device according to claim 3, which is characterized in that step 1)
In, Na2WO4.2H2O and (NH4)2SO4Mass ratio be 3.3:2.
5. the preparation method of quasi- solid-state tungstic acid electrochromic device according to claim 3, which is characterized in that step 1)
The WO3In mixed solution, WO3Mass fraction is 0.5%.
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